San Jose State University SJSU ScholarWorks Master's Theses Master's Theses and Graduate Research Fall 2010 Organocatalytic decomposition of poly(ethylene terephthalate) using triazabicyclodecene proposal Julien Matsumoto Lecuyer San Jose State University Follow this and additional works at: https://scholarworks.sjsu.edu/etd_theses Recommended Citation Lecuyer, Julien Matsumoto, "Organocatalytic decomposition of poly(ethylene terephthalate) using triazabicyclodecene proposal" (2010). Master's Theses. 3873. DOI: https://doi.org/10.31979/etd.c3kc-xcdz https://scholarworks.sjsu.edu/etd_theses/3873 This Thesis is brought to you for free and open access by the Master's Theses and Graduate Research at SJSU ScholarWorks. It has been accepted for inclusion in Master's Theses by an authorized administrator of SJSU ScholarWorks. For more information, please contact [email protected]. ORGANOCATALYTIC DECOMPOSITION OF POLYETHYLENE TEREPHTHALATE USING TRIAZABICYCLODECENE A Thesis Presented to The Faculty of the Department of Chemical and Materials Engineering San Jose State University In Partial Fulfillment of the Requirements for the Degree Master of Science by Julien Matsumoto Lecuyer December 2010 © 2010 Julien Matsumoto Lecuyer ALL RIGHTS RESERVED ORGANOCATALYTIC DECOMPOSITION OF POLYETHYLENE TEREPHTHALATE USING TRIAZABICYCLODECENE by Julien Lecuyer APPROVED FOR THE DEPARTMENT OF CHEMICAL & MATERIALS ENGINEERING SAN JOSÉ STATE UNIVERSITY August 2010 Dr. Melanie McNeil Department of Chemical & Materials Engineering Dr. Richard Chung Department of Chemical & Materials Engineering Dr. James Hedrick IBM Almaden Research Center Dr. Kazuki Fukushima IBM Almaden Research Center ABSTRACT ORGANOCATALYTIC DECOMPOSITION OF POLYETHYLENE TEREPHTHALATE USING TRIAZABICYCLODECENE This study focuses on the organocatalytic decomposition of polyethylene terephthalate (PET) using 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) to form a diverse library of aromatic amides. The reaction scheme was specifically designed to use low reaction temperatures (>150 oC) and avoid using solvents during the reaction to provide a more environmentally friendly process. Of all the amines tested, PET aminolysis with aliphatic and aromatic amines demonstrated the best performance with yields higher than 72%. PET aminolysis with click functionalized and non-symmetric reagents facilitated attack on certain sites on the basis of reactivity. Finally, the performance of the PET degradation reactions with secondary amine and tertiary amine functionalized reagents yielded mixed results due to complications with isolating the product from the crude solution. Four of the PET-based monomers were also selected as modifiers for epoxy hardening to demonstrate the ability to convert waste into monomers for high-value applications. The glass transition temperatures, obtained using differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) of the epoxy composite samples treated with the PET-based monomers, were generally higher in comparison to the samples cured with the basic diamines due to the hydrogen bonding and added rigidity from the aromatic amide group. Developing these monomers provides a green and commercially viable alternative to eradicating a waste product that is becoming an environmental concern. ACKNOWLEDGEMENTS First and foremost, I would like to sincerely thank Dr. Jim Hedrick and Dr. Kazuki Fukushima for providing me the opportunity to work on such a remarkable project. I cannot explain how much their humor, patience, and willingness to help has meant to me; for that, I will forever be in their debt. I would also like to thank Dr. Melanie McNeil, my advisor, and Dr. Richard Chung for helping me reach my potential as an engineer through the completion of this project. In addition, I would like to thank the following people for their appreciated contributions to this project: Dr. Teddie Magbitang, Dr. Dolores Miller, Dr. Joseph Sly, Dr. Young-Hye Na, Dr. Hans Horn, Dr. Julia Rice, Dr. Robert Allen, Dr. Robert Miller, Victor Lee, Neil Peters, and the members of KACST. I also owe a great deal of gratitude toward San Jose State University and IBM Almaden Research Center for providing me with the environment necessary for me to succeed. Finally, I would like to dedicate this thesis to my parents. I would not be where I am today without their emotional and financial support, especially during my years as an undergraduate and graduate student. I will never be able to thank them enough for everything they have done for me. v TABLE OF CONTENTS CHAPTER ONE INTRODUCTION .................................................................................. 1 1.1 Green Chemistry ........................................................................................... 1 1.2 Production of Polyethylene Terephthalate ................................................... 3 1.3 Recycling of Polyethylene Terephthalate ..................................................... 5 CHAPTER TWO LITERATURE REVIEW ...................................................................... 9 2.1 Evolution of Organocatalysts ..................................................................... 10 2.1.1 Metal Catalysts ............................................................................................10 2.1.2 Pyridine-based and Imidazolidone-based Organocatalysts .........................11 2.1.3 Bifunctional Organocatalysts ......................................................................16 2.1.4 Amidine-based and Guanidine-based Organocatalysts ...............................18 2.2 Applications of Aromatic Amide/Ester Compounds .................................. 22 2.2.1 Epoxy Hardening .........................................................................................23 2.2.2 Interfacial Polymerization and Desalination Membranes ...........................27 2.2.3 Applications in Specialty Polymers ............................................................29 2.3 Economic Analysis ..................................................................................... 30 2.3.1 Economics of PET Degradation Via Organocatalysis ................................31 2.3.2 Economics of Incorporating PET-derived Diamines for Epoxy Hardening ....................................................................................................33 2.4 Literature Review Summary ...................................................................... 34 CHAPTER THREE PROJECT OBJECTIVES ................................................................ 36 CHAPTER FOUR MATERIALS AND METHODS ....................................................... 38 4.1 Organocatalytic Decomposition of Polyethylene Terephthalate ................ 38 4.1.1 Materials ......................................................................................................40 4.1.2 Experimental Procedure for PET Decomposition .......................................41 4.1.3 PET Decomposition Incorporating Reused Reagents .................................53 4.2 Epoxy Hardening Process Incorporating PET-derived Amides ................. 54 4.2.1 Epoxy Hardening Materials .........................................................................54 4.2.2 Epoxy Preparation for Thermal Analysis ....................................................56 4.3 Methods and Materials Summary .............................................................. 61 vi CHAPTER FIVE PET AMINOLYSIS RESULTS .......................................................... 62 5.1 H-NMR Analysis for PET-Derived Monomers ......................................... 64 5.2 Performance Analysis of PET Aminolysis Reactions ................................ 65 5.2.1 PET Aminolysis with Aliphatic and Aromatic-Containing Diamines ........65 5.2.2 PET Aminolysis with Non-Symmetric Amines ..........................................68 5.2.3 PET-Aminolysis with Click-Functionalized and Secondary Amines .........70 5.2.4 PET Aminolysis with Tertiary-Functionalized Amines ..............................72 5.3 Recycling of Amine Reagents for PET-Aminolysis .................................. 75 5.4 Discussion .................................................................................................. 80 5.4.1 Environmental Significance of Developing PET-Based Monomers ...........80 5.4.2 Process Optimization ...................................................................................81 5.4.3 Importance of Properties PET-Based for Potential Applications ................82 CHAPTER SIX PET-DIAMINE RESULTS AS EPOXY HARDENING MODIFIERS ..................................................................................................................... 84 6.1 Differential Scanning Calorimeter Results ................................................. 85 6.2 Dynamic Mechanical Analysis Results ...................................................... 88 6.2.1 PETED Composite DMA Results ...............................................................89 6.2.2 PETmX Composite DMA Results ..............................................................90 6.2.3 PETDAMDPA Composite DMA Results ...................................................92 6.2.4 PETDETA Composite DMA Results ..........................................................93 CHAPTER SEVEN CONCLUSIONS AND FUTURE WORK ...................................... 95 REFERENCES ................................................................................................................. 98 vii LIST OF TABLES Table 1. 12 principles